CN101903419B - Fast activating catalyst - Google Patents
Fast activating catalyst Download PDFInfo
- Publication number
- CN101903419B CN101903419B CN2008801219822A CN200880121982A CN101903419B CN 101903419 B CN101903419 B CN 101903419B CN 2008801219822 A CN2008801219822 A CN 2008801219822A CN 200880121982 A CN200880121982 A CN 200880121982A CN 101903419 B CN101903419 B CN 101903419B
- Authority
- CN
- China
- Prior art keywords
- chromium
- alkali
- polymkeric substance
- described method
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 230000003213 activating effect Effects 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000011651 chromium Substances 0.000 claims abstract description 50
- 230000004913 activation Effects 0.000 claims abstract description 40
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 35
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000032683 aging Effects 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 48
- 239000003513 alkali Substances 0.000 claims description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 25
- 150000001336 alkenes Chemical class 0.000 abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 41
- 238000001994 activation Methods 0.000 description 39
- 239000000017 hydrogel Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 18
- 238000000746 purification Methods 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- -1 aluminophosphates Chemical compound 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000007420 reactivation Effects 0.000 description 6
- 238000000518 rheometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007596 consolidation process Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910002028 silica xerogel Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012725 vapour phase polymerization Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ZNPMVKGXABWZAA-UHFFFAOYSA-N benzoic acid;chromium Chemical compound [Cr].OC(=O)C1=CC=CC=C1 ZNPMVKGXABWZAA-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- QZYJCTSSGJVQOT-UHFFFAOYSA-N chromium pyrrolidin-2-one Chemical compound [Cr].N1C(CCC1)=O QZYJCTSSGJVQOT-UHFFFAOYSA-N 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- CNIGXAJYMNFRCZ-UHFFFAOYSA-K butanoate;chromium(3+) Chemical compound [Cr+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O CNIGXAJYMNFRCZ-UHFFFAOYSA-K 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical compound [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KDPMIBMNNGCWTF-UHFFFAOYSA-N C(CCC)O.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical class C(CCC)O.CC1(CC(C(=O)O)=CC=C1)C(=O)O KDPMIBMNNGCWTF-UHFFFAOYSA-N 0.000 description 1
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021562 Chromium(II) fluoride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- PSMVUAUGXIFRFF-UHFFFAOYSA-N [Cr].C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cr].C1(=CC=CC=C1)C1=CC=CC=C1 PSMVUAUGXIFRFF-UHFFFAOYSA-N 0.000 description 1
- JBCJJENNWZWMGZ-UHFFFAOYSA-N [Cr].CC(C)c1ccccc1 Chemical compound [Cr].CC(C)c1ccccc1 JBCJJENNWZWMGZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RMXTYBQNQCQHEU-UHFFFAOYSA-N ac1lawpn Chemical compound [Cr]#[Cr] RMXTYBQNQCQHEU-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- VQRDICPZWTXYIK-UHFFFAOYSA-N chloric acid chromium(3+) Chemical compound [Cr+3].Cl(=O)(=O)O VQRDICPZWTXYIK-UHFFFAOYSA-N 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- KULZLSHMXVZRKE-UHFFFAOYSA-N chromium perchloric acid Chemical compound [Cr].Cl(=O)(=O)(=O)O KULZLSHMXVZRKE-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- RYPRIXSYXLDSOA-UHFFFAOYSA-L chromium(2+);sulfate Chemical compound [Cr+2].[O-]S([O-])(=O)=O RYPRIXSYXLDSOA-UHFFFAOYSA-L 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- IVKVYYVDZLZGGY-UHFFFAOYSA-K chromium(3+);octadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O IVKVYYVDZLZGGY-UHFFFAOYSA-K 0.000 description 1
- SCCNXKACLAJZAP-UHFFFAOYSA-N chromium(3+);pyrrol-1-ide Chemical compound [Cr+3].C=1C=C[N-]C=1.C=1C=C[N-]C=1.C=1C=C[N-]C=1 SCCNXKACLAJZAP-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910000334 chromium(II) sulfate Inorganic materials 0.000 description 1
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- RNFYGEKNFJULJY-UHFFFAOYSA-L chromium(ii) fluoride Chemical compound [F-].[F-].[Cr+2] RNFYGEKNFJULJY-UHFFFAOYSA-L 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 229940109126 chromous chloride Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- BMSDTRMGXCBBBH-UHFFFAOYSA-L diiodochromium Chemical compound [Cr+2].[I-].[I-] BMSDTRMGXCBBBH-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B01J35/615—
-
- B01J35/638—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Catalysts (AREA)
- Silicon Compounds (AREA)
Abstract
A method of preparing a catalyst comprising aging a silica support in an alkaline solution to produce an alkaline aged silica support, removing at least a portion of the alkaline solution from the alkaline aged silica support to produce a dried silica support, and activating the silica support to produce a catalyst composition, wherein alkaline aging lowers the surface area of the silica support to less than about 50% of the original value and wherein activation of the silica support is carried out in batches of equal to or greater than about 500 lbs for a time period of less than about 8 hours. A method of preparing a polymer comprising alkaline aging a silica support material, adding chromium to the silica support material prior to the alkaline aging, after the alkaline aging, or both to form a chromium-silica support, rapidly activating the chromium-silica support produce an activated olefin polymerization catalyst, contacting the activated olefin polymerization catalyst with at least one monomer in a reaction zone under conditions suitable to produce a polymer, and recovering the polymer.
Description
Technical field
The catalyzer that present disclosure relates generally to comprise chromium and carrier with and preparation and activation method.
Background technology
The chromium loaded catalyst is used to the polymerization of olefin polymer.The chromium mfr is through placing chromium this catalyzer of preparation on carrier such as silicon-dioxide or the silica-titania.Carrier helps to stablize the active of chromium and allow this catalyzer to send to the buyer with inactive form.In case catalyzer arrives at the polymer manufacture place, it is activated and is used for polymerization technique.Big and expensive equipment is adopted in the activation of these catalyzer usually, and it is used to the nonactive compsn of long heat treatment at high temperature.
Polymkeric substance mfr's throughput receives several factors limit, and one of them is the required time of catalyst activation.Any improvement on the amount of catalyst activation required time and/or the activable catalyzer of random time can improve the efficient of whole polymer manufacture technology.Therefore there is urgent demand to developing improved catalyst activation process.
The invention summary
Herein disclosed is the method for preparing catalyzer; It is included in the silica supports that wears out in the basic soln to produce alkali aged silica supports; From alkali aged silica supports, remove at least a portion basic soln to produce the exsiccant silica supports; And the activation silica supports is to produce catalyst composition; Wherein alkali is aging makes the surface-area of silica supports reduce to the about below 50% of original value, and wherein the activation of silica supports is carried out less than about 8 hours time durations with the batch that is equal to or greater than about 500 pounds (1bs).
This paper also discloses the method for preparing polymkeric substance; It comprises the alkali silica support materials that wears out; With chromium before alkali is aging, alkali aging after or join silica support materials with formation chromium-silica supports under two kinds of situation; Fast activating chromium-silica supports is produced the activatory olefin polymerization catalysis, the activatory olefin polymerization catalysis is contacted being suitable for producing under the condition of polymkeric substance at reaction zone with at least a monomer, and the recovery polymkeric substance.
This paper further discloses the method for preparing polymkeric substance; It comprises the alkali silica supports material that wears out; With chromium before alkali is aging, alkali aging after or join silica support materials with formation chromium-silica supports under two kinds of situation; And fast activating chromium-silica supports produces the activatory olefin polymerization catalysis, and wherein fast activating chromium-silica supports comprises and is equal to or greater than under about 700 ℃ temperature heating less than about 8 hours time durations.
This paper further discloses the method for preparing catalyzer; It comprises provides the supported chrome compsn; Chemistry consolidation (chemically fuseing) carrier substance is with generation consolidation supported chrome compsn, and fast activating precursor catalyst composition is to produce the activatory olefin polymerization catalysis.
This paper further discloses the method for preparing catalyzer; It is included in the silica hydrogel that wears out in the basic soln to produce alkali aged silica hydrogel; From alkali aged silica hydrogel, remove at least a portion basic soln to produce silica xerogel; And the activation silica xerogel to be to produce catalyst composition, and wherein catalyst composition has less than about 300m
2The surface-area of/g and wherein the activation of silica xerogel carry out less than about 8 hours time durations with the batch that is equal to or greater than about 500lbs.
Description of drawings
In order more fully to understand present disclosure, with reference now to following summary and combine accompanying drawing and detailed description, wherein similar reference number is represented similar part.
Fig. 1 is the schema for preparing the method for catalyzer.
Fig. 2 is for the sample from embodiment 1, and melt index is as the function plotting of the productivity under each catalytic amount.
Fig. 3 is for the sample from embodiment 1, and HLMI/MI is as the function plotting of the ratio of the melt index under each catalytic amount.
Fig. 4 is for the sample from embodiment 2, and melt index is as the function plotting of the productivity under each residence time.
Fig. 5 is for the sample from embodiment 2, and HLMI/MI is as the function plotting of the melt index under each residence time.
Detailed Description Of The Invention
---being at present known or existing---although the illustrative enforcement of one or more embodiments is provided below should be appreciated that at the very start, no matter disclosed system and/or method can adopt any amount of technology implements.Present disclosure never should be limited to illustrative embodiment, accompanying drawing and the technology of elucidated hereinafter; It comprises illustrative design and embodiment that this paper describes and illustrates, but can the scope of accompanying claims with and the four corner of Equivalent in make amendment.
Herein disclosed is the method for preparing catalyzer, it comprises the contact compsn, and the contact compsn is included in the silica supports that wears out in the basic soln to produce alkali aged silica supports; Remove at least a portion basic soln to produce the exsiccant silica supports from alkali aged silica supports; And the activation silica supports is to produce catalyst composition.When comparing with the compsn that does not have preparation under the alkaline purification, said silica supports reactivation process subsequently can be carried out the less time.Hereinafter, through this paper disclosed method preparation and catalyst composition (RACCs) be called as fast activating with the postactivated catalyst composition.Each catalyst component and preparation and activation method have been described among this paper in more detail.
In one embodiment, RACC comprises carrier.Carrier can be inorganic oxide such as silicon-dioxide or silica-titania.Carrier can further comprise other composition that can not have a negative impact to RACC, such as aluminum oxide, aluminophosphates, boron oxide, Natural manganese dioxide, Thorotrast, zirconium white, cerium dioxide, clay, zeolite or its combination.
In one embodiment, carrier comprises silicon-dioxide.Silica supports can be used prepared by any suitable process.For example, silica supports can prepare through alkali metal silicate aqueous solution is contacted with acid to form silica hydrogel.
In an optional embodiment, carrier comprises silica-titania.The silica-titania carrier can adopt any suitable method such as silicon-dioxide and titanium-containing compound such as TiCl
3Or TiCl
4Cogelled, heterogeneous co-precipitation and surface impregnation prepare.In one embodiment, the silica-titania carrier can have scope from about 250m
2/ g is to about 600m
2The surface-area of/g and scope pore volume from about 1.0cc/g to about 3.0cc/g.
Carrier (for example silicon-dioxide or silicon dioxide and titanium dioxide) can exist with the amount of about 90 per-cents (%) of being equal to or greater than the RACC gross weight, is equal to or greater than approximately 95% alternatively, is equal to or greater than about 98% alternatively.
In one embodiment, RACC comprises chromium, and it can contact with carrier and be incorporated among the RACC through containing chromium cpd.Contain chromium cpd and can be the compound that one or more comprise sexavalence oxidation state chromium (hereinafter Cr (VI)) or comprise the material that is suitable for changing into Cr (VI).In one embodiment, contain chromium cpd and comprise water soluble ge cpd; Alternatively, contain chromium cpd and comprise the soluble chromium cpd of hydrocarbon.Containing chromium cpd can be chromium (II) compound, chromium (III) compound or its combination.Suitable chromium (III) compound includes but not limited to carboxylic acid chromium, chromium naphthenate, hafnium halide, pyrrolidone chromium (chromium pyrrolide), phenylformic acid chromium, two ketonize chromium, chromium nitrate, chromium sulphate or its combination.Concrete chromium (III) compound includes but not limited to isocaprylic acid chromium (III), 2; 2; 6,6-dipivaloylmethane chromium (III), chromium naphthenate (III), chromium chloride (III), three (2 ethyl hexanoic acid) chromium (III), chromium fluoride, oxygen-2 ethyl hexanoic acid chromium (III), Dichloroethyl caproic acid chromium (III), chromium acetylacetonate (III), chromium acetate (III), chromium butyrate (III), PIVALIC ACID CRUDE (25) chromium (III), LAURIC ACID 99 MIN chromium (III), chromium sulphate (III), chromium+oxalic acid (III), phenylformic acid chromium (III), pyrrolidone chromium (III), perchloric acid chromium (III), chloric acid chromium (III) or its combination.Suitable chromium (II) compound includes but not limited to Chromous Fluoride, chromous chloride, chromous bromide, chromous iodide, two (2 ethyl hexanoic acid) chromium (II), chromium acetate (II), chromium butyrate (II), PIVALIC ACID CRUDE (25) chromium (II), LAURIC ACID 99 MIN chromium (II), chromium stearate (II), chromium+oxalic acid (II), phenylformic acid chromium (II), pyrrolidone chromium (II), chromous sulfate or its combination.The instance that contains chromium cpd that other is suitable comprises the tertiary butyl chromate in the hydrocarbon liquid; Chromium trioxide in the water; Chromium acetate in the water; Chromium nitrate in the alcohol; The zeroth order organo-chromium compound is such as π bonding chromium complex, for example cumene chromium and biphenyl chromium; Or its combination.π bonding chromium complex is described in U.S. Patent number 3,976, and in 632, it incorporates this paper into its full content by reference.
Based on the final weight of RACC, the amount that chromium can about 0.1% to about 10% is present among the RACC about alternatively 0.2% to about 2%, perhaps about 1%.
What describe among Fig. 1 is the embodiment of method 100 of the RACC of preparation type disclosed herein.With reference to figure 1, in one embodiment, method 100 can begin in the formation of square frame 110 with hydrogel.Hydrogel is insoluble silicate chain network and to can be used as water be that the colloidal gel of dispersion medium is found in the water.In one embodiment, hydrogel is made up of carrier substance (for example silicon-dioxide or silica-titania).Hereinafter, for simplicity, present disclosure will concentrate on the application of silica hydrogel, although other type of hydrogel as herein described (for example silica-titania) also is taken into account.
In one embodiment, hydrogel comprises silicon-dioxide.Silica hydrogel can form through alkalimetal silicate such as water glass is contacted such as sulfuric acid with acid.This contact for example can be carried out under appropriate condition through the mode of mixing or stir.Silica hydrogel further water or with the acid of any suitable compound such as ammonium salt (for example an ammonium nitrate etc.) or dilution further washing with the alkali metal content of minimizing silica hydrogel.Washing can be carried out repeatedly perhaps until the result who reaches user expectation.
In the square frame 120, silica hydrogel then can about 60 ℃ to about 90 ℃, or about 70 ℃ to about 85 ℃, perhaps contact with the basic soln that comprises one or more basic cpds (for example alkali, damping fluid) of pH about 8 to about 13, alternatively about 9 to about 12, alternatively about 9 to about 10 under the about 80 ℃ temperature.That the processing of silica hydrogel is called as alkali is aging through under condition described herein, being exposed to basic soln.Basic soln can comprise any component, and said any component provides pH value of solution in the open scope and compatible with other composition of compsn.For example, basic soln can comprise volatile caustic, Pottasium Hydroxide, sodium hydroxide, hydroxide trialkyl ammonium, water glass etc.Can utilize other suitable compound and amount that the solution in the open pH scope is provided effectively.
The alkali of silica hydrogel is aging can to carry out during the time enough; About below 50% with the original value of the surface-area of silica supports being reduced to the surface-area that does not carry out other similar substance of alkali aged; Original value is about below 45% alternatively; Original value is about below 40% alternatively, and original value is about below 35% alternatively.For the surface-area of measuring base-material silicon-dioxide or Cr/ silicon-dioxide, xerogel is at first dry down to remove adsorbed components at 200-400 ℃.For example, carrier can comprise silica supports, if its drying under its original (it is aging not carry out alkali) state will produce about 600m
2The surface-area of/g.Yet alkali is aging can reduce to about 300m with the surface-area of carrier
2Below/the g, about alternatively 280m
2Below/the g, about alternatively 250m
2Below/the g, about alternatively 225m
2Below/the g.In one embodiment, alkali is aging carries out about 1 hour to about 24 hours, or about 2 hours to about 10 hours, perhaps about 3 hours about 6 hours time durations extremely.
In the square frame 130, comprise that the compsn of silica hydrogel and alkaline aqueous solution can further be processed from compsn, to remove all or a part of aqueous solution.For example, compsn can adopt standard technique such as thermal treatment, jet drying perhaps to contact with the volatility liquid organic solvent and carry out drying.The instance of volatility liquid organic solvent comprises MIBK, ETHYLE ACETATE, sec-butyl alcohol, n-propyl alcohol, butyraldehyde, diisobutyl ether, isopropyl acetate, 3-methyl isophthalic acid-butanols, 1-amylalcohol, 2-amylalcohol, 1-hexanol or its combination without limitation.The drying of silica species can change into silica xerogel with silica hydrogel, and gained alkali aged, exsiccant silica species are hereinafter referred to as precursor catalyst composition (PCC).In the square frame 140, PCC can be with postactivated to form RACC.The activation of precursor composition can will be carried out like this paper back with describing.
Chromium can be added in the precursor catalyst composition (for example silica supports, silica-titania carrier) during building-up process any time.In one embodiment, silica supports (for example hydrogel and/or xerogel) can be before alkali be aging, during and/or afterwards further with contain chromium cpd and contact.In one embodiment, silica hydrogel and/or xerogel before alkali is aging with contain chromium cpd and contact; Alternatively, experience alkali aged silica hydrogel and/or xerogel can contain chromium cpd with this paper aforementioned type and contact after alkali is aging; Or its combination.Cr-silica species or carrier are containing silica supports and are containing chromium cpd and contact the back and form.In one embodiment, the Cr-silica hydrogel is worn out by alkali and is converted to silicon-dioxide-Cr xerogel subsequently.
In one embodiment, PCC is activated to produce active catalyst, active polymerizing catalyst alternatively.The PCC of present disclosure various types of acvator equipment capable of using carry out activation.Can adopt any container or device activation PCC, it comprises for example rotary calcining stove, static pan dryer or fluidized-bed.Such equipment can static schema, intermittent mode or continuous mode operation.For static state or intermittent mode, contain the container of catalyst bed or install each stage of preface experience reactivation process successively.For continuous mode, process stage can occur in a series of zones, and wherein PCC passes activation equipment through these zones on its path.
In one embodiment, PCC carries out activation in the fluidized-bed activation equipment.In the fluidized-bed activation equipment, gas can upwards flow and pass the end fittings that comprise many apertures, places PCC on it.Gas can comprise all cpds that produces the expectation processing condition.When gas flow, PCC can be blended in the gas, produces fluid-like stream.This often is called as fluidisation (fluidization) or fluidisation (fluidizing).
Activation can further be included in one or more stages PCC is heated to preferred temperature.As used herein, term " stage " is meant that heating PCC is to preferred temperature and keep this temperature for some time.Carry out and can comprise inclination rise time of arriving preferred temperature and PCC is remained on certain residence time of this temperature when a stage can be worked as PCC and is in a fixed position or through PCC being moved through each position.For two or more stages, two or more inclination rise time, two or more preferred temperature and two or more residence time will be arranged.Tilting the rise time can be identical or different, and the rise time of for example tilting can be that (the for example environment of preheating) of moment is extremely about below 3 hours.
These materials (for example 100 to 1500 pounds) that the big volume of industrial activation general using of the PCC of type described herein---is called as in batches commercial---and the long-time slowly heating of needs these materials to high temperature (for example 800 ℃).In one embodiment, the alkali weathering process is undertaken by the commercial catalysts mfr in the commercial catalysts producing apparatus, and catalyzer betransported, and reactivation process is undertaken by the commercial polymer producer in commercial polymerization process unit.In one embodiment; PCC carries out activation in batches with commerce, and wherein each batch comprises and to be equal to or greater than about 750lbs alternatively by the catalyzer that is equal to or greater than about 500lbs; Be equal to or greater than about 1000lbs alternatively, be equal to or greater than about 1250lbs alternatively.PCC activatory temperature (or a plurality of) can be regulated to reach the result of user expectation.For example, temperature (or a plurality of) scope can be about 400 ℃ to about 1000 ℃, and about alternatively 600 ℃ to about 900 ℃, about alternatively 750 ℃ to about 900 ℃.The activation of the PCC of preparation as described herein can be carried out fast, for example when with the other similar compsn comparison of not experiencing processing described herein, carries out with the time quantum that reduces.In one embodiment, PCC can be in about time below 8 hours of activation under the maximum temperature, and is about alternatively below 7 hours; About alternatively below 6 hours; About alternatively below 5 hours, about alternatively below 4 hours, about alternatively below 3 hours; About alternatively below 2 hours, about alternatively below 1 hour.If adopt two or more stages, total residence time is the summation of all residence time in stage under the maximum temperature.Thermal activation in stage is further described at U.S. Patent number 4,022, and 580 and in the U.S. Patent Application Publication No. 2005/0255987A1 that announced on November 17th, 2005, its each piece of writing is incorporated this paper into its full content.
Do not hope bound by theory, the activation of PCC causes the dehydroxylation and the annealing of carrier substance, and it can further reduce surface-area.Therefore, if the aging step of alkali is enhanced and suitably regulates, then can obtain some and the long-time identical benefit of high-temperature activation.Therefore, enhanced alkali is aging can allow short soak time, the activation efficiency of increase and higher equipment yield.
Activation causes that also the chromium chromium (Cr (III)) of any trivalent form is oxidized to sexavalence form (Cr (VI)) and Cr (VI) form stable then.As used herein, the reactivation process that is meant the catalyzer that produces Cr (VI) form " stablized " in term.Reactivation process can change into Cr (VI) with about 10 to about 100% Cr (III); Perhaps about 30 to about 80%, perhaps about 35 to about 65%, and produce about 0.1 to about 1% Cr (VI); About 0.2 to about 0.9%, perhaps about 0.3 to about 0.65%.
In one embodiment, when when not having under the alkaline purification the other similar catalyzer comparison of preparation, the RACC of type described herein presents the surface-area of minimizing and the aperture of increase.In some embodiments, when when not having under the alkaline purification the other similar catalyzer comparison of preparation, the RACC of type described herein presents the pore volume of increase.For example, the surface area of RACC can be about 100 square metres of every gram (m
2/ g) to about 600m
2/ g, perhaps about 200m
2/ g is to about 400m
2/ g, perhaps about 250m
2/ g is to about 350m
2/ g.In another embodiment; The pore diameter range of RACC be about 50 dusts
to about 400
or about 100
to about 350
or about 200
to about 300
in another embodiment; The pore volume scope of RACC is that about 1 cubic centimetre of every gram (cc/g) is to about 3cc/g; Perhaps approximately 1.2cc/g is to about 2.5cc/g, and perhaps about 1.5cc/g is 2cc/g extremely approximately.
Catalyzer of the present invention and resin (being RACC) are intended to be used to adopt any olefine polymerizing process of various polymerization reactors.As used herein, " polymerization reactor " comprises that any ability polymerization of olefin monomers is to produce the polymerization reactor of homopolymer or multipolymer.This homopolymer and multipolymer are called as resin or polymkeric substance.Various reactor drums comprise those that can be called as intermittence, slurry, gas phase, solution, high pressure, tubulose or autoclave reactor.Gas-phase reactor can comprise fluidized-bed reactor or multistage horizontal reactor.Slurry-phase reactor can comprise vertical or horizontal loop.High-pressure reactor can comprise autoclave or tubular reactor.Type of reactor can comprise intermittently or continuous processing.Continuous processing can adopt intermittently or continuous product flows out.Technology also can comprise the partly or entirely directly recycling of unreacted monomer, unreacted comonomer and/or thinner.
Polymerization reactor system of the present invention can comprise a plurality of reactor drums of a kind of reactor drum of a system or identical or different type.The production of polymkeric substance can be included in by the several stages in interconnective two the discrete polymerization reactors of transfer equipment at least in a plurality of reactor drums, and said transfer equipment makes the polymkeric substance that will from first polymerization reactor, obtain be transferred to second reactor drum becomes possibility.The polymerizing condition of one of reactor drum desired can be different with the operational condition of other reactor drum.Alternatively, the polymerization in a plurality of reactor drums can comprise and transfers to the subsequent reaction device to continue polymerization from a reactor drum with polymkeric substance is manual.A plurality of reactor assemblies can comprise any following combination, and it includes but not limited to the combination of the combination of a plurality of loop reactors, a plurality of gas reactor, loop and gas reactor, a plurality of high-pressure reactor or high pressure and loop and/or gas reactor.But a plurality of reactor drum serial or parallel connection operations.
According to an aspect of the present invention, polymerization reactor system can comprise at least one loop slurry reactor, and it comprises vertical or horizontal loop.Monomer, thinner, catalyzer and randomly any comonomer can be continuously fed into the loop reactor that polymerization takes place.Usually, continuous processing can comprise introduces monomer, catalyzer and thinner continuously in polymerization reactor, and from this reactor drum, removes the suspension-s that comprises polymer beads and thinner continuously.Reactor effluent can be flashed from the liquid that comprises thinner, monomer and/or comonomer, to remove solid polymer.Various technologies can be used for this separating step, and it includes but not limited to comprise the flash distillation of heating and decompression arbitrary combination; In cyclonic separator or wet cyclone, pass through the separation of whirlwind effect; Or through spinning.
Typical slurry polymerization process (also being called as the particle forming method) is disclosed for example U.S. Patent number 3,248,179,4,501,885,5,565; 175,5,575,979,6,239,235,6; In 262,191 and 6,833,415, wherein each piece of writing is incorporated this paper into by reference with its full content.
The suitable diluents of using in the slurry polymerization includes but not limited to be by polymerization single polymerization monomer with under reaction conditions the hydrocarbon of liquid.The instance of suitable diluents includes but not limited to hydrocarbon such as propane, hexanaphthene, Trimethylmethane, normal butane, Skellysolve A, iso-pentane, neopentane and normal hexane.Some loop polymerization reactions can take place down in the body phase condition (bulk condition) of not using thinner.Embodiment is the polymerization of propylene monomer, and like U.S. Patent number 5,455,314 is disclosed, and it incorporates this paper into by reference with its full content.
According to of the present invention also on the other hand, polymerization reactor can comprise at least one Gas-phase reactor.This type systematic can be applicable under the polymerizing condition under the situation that catalyzer exists circulation continuously through fluidized-bed, contain one or more monomeric continuous recycle streams.Recycle stream can be discharged also from fluidized-bed, and recycling is back to reactor drum.Simultaneously, polymer product can be discharged from reactor drum, and new or fresh monomer can be added to replace monomer polymerized.These Gas-phase reactor can comprise the process of the rapid vapour phase polymerization of multistep of alkene, wherein alkene at least two independent vapour phase polymerization zones with vapour phase polymerization, and polymer feed to the second zone of convergency of containing catalyzer that will form in first zone of convergency simultaneously.One type of Gas-phase reactor at U.S. Patent number 5,352, and open in 749,4,588,790 and 5,436,304, wherein each all incorporates this paper by reference into.
According to of the present invention also on the other hand, pressure polymerization reactor can comprise tubular reactor or autoclave reactor.Tubular reactor can have several zones, to wherein adding fresh monomer, initiator or catalyzer.Monomer can be entrained in the inertia gaseous stream and in a zone of reactor drum and introduce.Initiator, catalyzer and/or catalyst component can be entrained in the gaseous stream and in another zone of reactor drum and introduce.Gas stream can be mixed for polymerization.Suitably application of heat and pressure are to obtain optimum polymerizating reacting condition.
According to another aspect of the invention, polymerization reactor can comprise solution polymerization reactor, and wherein monomer contacts with catalyst composition through suitable stirring or other method.Can use the carrier that comprises inertia organic thinner or excess monomer.If expectation can make monomer contact with catalytic reaction products with gas phase existing or not existing under the situation of fluent material.The zone of convergency is maintained at the temperature and pressure that causes that polymers soln forms in reaction medium.Can use stirring and control and keep the polyblend of the homogeneous that runs through the zone of convergency to obtain better temperature.Utilize appropriate means with the dissipation polymerization exotherm.
Be suitable for polymerization reactor of the present invention and can further comprise the feeding system of at least one starting material feeding system, at least one catalyzer or catalyst component and/or any combination of at least one polymer recovery system.The suitable reactor assembly of the present invention can further comprise feed purification, catalyst stores and preparation, extrudes, the system of reactor cooling, polymer recovery, fractionation, recycling, storage, loading, lab analysis and process control.
Be Controlled is used for polymerization efficiency and provides the condition of resin properties to comprise temperature, pressure and various concentration of reactants.Polymerization temperature can influence catalyst productivity, polymericular weight and MWD.Suitable polymerization temperature can be any temperature that is lower than the depolymerization temperature according to the Gibbs free energy equation.Normally, this temperature comprises about 60 ℃ to about 280 ℃, for example, and about 70 ℃ to about 110 ℃, it depends on the type of polymerization reactor.
Suitable pressure also will change according to reactor drum and polymeric type.The pressure of the liquid polymerization in loop reactor is normally less than 1000psig.The pressure of vapour phase polymerization is usually at about 200-500psig.High pressure polymerisation in tubulose or the autoclave reactor is generally about 20,000 to 75, the 000psig operation.Polymerization reactor also can operate in the supercritical range that occurs in higher usually temperature and pressure.The running that exceeds Pressure/Temperature figure stagnation point (supercritical phase) can provide advantage.
Various concentration of reactants can be controlled to produce the resin with some physics and mechanical properties.The whole purposes product of expectation is by resin formation, and forms the desired resin properties of method decision of this product.Mechanical properties comprises stretching, bending, bump, creep, stress relaxation and hardness test.Physical properties comprises density, molecular weight, MWD, melting temperature (Tm), second-order transition temperature, crystalline melting temperature, density, stereospecicity, crack growth, long chain branching and rheology measurement.
The concentration of monomer, comonomer, hydrogen, promotor, properties-correcting agent and electron donor is important when producing these resin properties.Comonomer is used to control product density.Hydrogen can be used for controlling molecular weight of product.Promotor can be used for alkylation, removes poisonous substance and control molecular weight.Properties-correcting agent can be used for controlling product characteristics and electron donor influences stereospecicity.In addition, the concentration of poisonous substance is minimized, because poisonous substance influence reaction and product characteristics.
Polymkeric substance or resin can be shaped as various goods, include but not limited to bottle, bucket, toy, household receptacle, utensil, film product, drum, fuel tank, pipe, geomembrane and lining.The whole bag of tricks these goods that can be used for being shaped include but not limited to blowing, extrusion molding, rotational molding, thermoforming, casting moulding or the like.After the polymerization, additive and properties-correcting agent can be added into polymkeric substance better processing to be provided and desired character is provided in end product in manufacturing processed.Additive comprises surface-modifying agent, such as slip(ping)agent, anti-hard caking agent, tackifier; All main anti-oxidants of inhibitor and secondary antioxidant; Pigment; Processing aid such as wax/oil and viton; And special-purpose additive such as fire retardant, static inhibitor, scavenging agent, absorption agent, odorant and degradation agents.
Catalyzer according to disclosure preparation can be used for the for example polymerization of terminal olefin of alkene.In one embodiment, RACC contacts with olefin polymerization at conversion zone (for example temperature, pressure etc.) under appropriate reaction conditions with one or more alkene.Straight or branched terminal olefin with 2 to 30 carbon atoms can be used as olefin feedstock.The specific examples of terminal olefin can comprise ethene, propylene, 1-butylene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene or the like.
The multipolymer of Natene and ethene and other monoolefine can use the catalyzer (being RACC) of preparation described herein to produce in the above described manner.In one embodiment, RACC is used to produce Natene, is high density polyethylene(HDPE) alternatively.The fluoropolymer resin of openly producing like this paper can use the technology such as extruding, blowing, injection molding, fiber sprinning, thermoforming and casting, is configured as goods or whole purposes article.For example, fluoropolymer resin can be extruded in flakes, and this sheet is thermoformed into whole purposes article then, such as container, cup, dish, tray, toy or other products assembly.The instance of other whole purposes article that can be formed by fluoropolymer resin comprises pipe, film, bottle, fiber or the like.
RACC can demonstrate and the other similar commeasurable polymerization activity of catalyzer that under the situation that lacks alkaline purification, prepares.Polymerization activity is meant the polymkeric substance gram number that every gram solid catalyst (g/g-h) of per hour charging is produced.In one embodiment, the polymerization activity that has of RACC is for being equal to or greater than about 1000g/g-h or being equal to or greater than about 2000g/g-h or being equal to or greater than about 2500g/g-h.
Hereinafter, disclosed polymer property characterizes with respect to the polymkeric substance that uses the other similar Preparation of Catalyst that under the situation of the alkaline purification that lacks type described herein, prepares.In one embodiment, the polymkeric substance that RACC produces has about 0.1 to about 10 melt index, about alternatively 0.2 to about 5, about alternatively 0.3 to about 1.5.Melt index (MI) is meant according to ASTM D 1238 and measures, and when when in 10 minutes, standing the power of 2160 grams for 190 ℃, can be extruded the amount of the polymkeric substance in the extrusion rheometer hole through 0.0825 inch diameter.In one embodiment, RACC can be used for production density greater than about 0.945cc/g, alternatively greater than about 0.950cc/g, alternatively greater than the about polymkeric substance of 0.955cc/g.
Use the polymkeric substance of the RACC preparation of type described herein also can show the high-load melt index of increase.High-load melt index (HLMI) is meant according to ASTM D 1238 and measures, when when standing the power of 21,600 grams for 190 ℃, and the flow velocity of the molten plastic resin through 0.0825 inch diameter hole.In one embodiment, RACC produce have high-load melt index be equal to or greater than about 10, be equal to or greater than about 50 polymkeric substance alternatively.
The polymkeric substance that the RACC of use this paper disclosed method methodology produces can further characterize the extrudate swelling that also can demonstrate reduction through the long chain branching that increases.Extrudate swelling is meant polymkeric substance expansible phenomenon on the direction of not expecting when the outlet through extrusion machine.In one embodiment; When comparing with the other similar catalyzer that under the situation of shortage alkaline purification, prepares, RACC produces has about 5% to about 50%, alternatively about 10% to about 30%, alternatively about 10% polymkeric substance to about 25% extrudate swelling.
The polymkeric substance that the RACC that uses methodology as herein described to prepare produces can further be characterized by the rheology width with reduction when comparing with the polymkeric substance that uses the other similar Preparation of Catalyst that lacks alkaline purification.The rheology width is meant newton-type and the width of the transitional region between the power law type shearing rate or the frequency dependence of polymer viscosity of polymkeric substance.The rheology width is the function that distributes the time of relaxation of fluoropolymer resin, itself so that be again the function of resinous molecular structure or structure.Adopt the Cox-Merz rule, the match of the flow curve that the rheology width produces in can testing through linearity-visco-elasticity dynamic oscillation frequency sweep and Carreau-Yasuda (CY) model of correction is calculated, and it can be represented by equation:
Wherein
E=viscosity (Pas)
A=rheology width parameter
T
ξ=time of relaxation (s) [position when being described in transitional region]
E
o=zero-shear viscosity (Pas) [definition newton's stable platform (Newtonian plateau)]
N=power law constant [the whole slope in definition high shear rate zone]
For the ease of model-fitting, power law constant remains on steady state value.The CY model is found in the derive meaning of parameter and the detailed description of explanation: C.A.Hieber and H.H.Chiang, Rheol. Acta, 28,321 (1989); C.A.Hieber and H.H.Chiang, Polym.Eng.Sci., 32,931 (1992); And R.B.Bird, R.C.Armstrong and O.Hasseger, Dynamics of Polymeric Liquids; Volume 1, Fluid Mechanics, 2nd Edition; John Wiley & Sons (1987), wherein each all incorporates this paper by reference into.In one embodiment; Use type described herein RACC preparation polymkeric substance when with use the situation that is lacking alkaline purification under during the polymkeric substance comparison of the other similar Catalyst Production for preparing, the CY-a value that has reduced be equal to or greater than about 5%, alternatively be equal to or greater than about 7%, be equal to or greater than about 10% alternatively.In one embodiment, use CY-a value that the polymkeric substance of the RACC preparation of type described herein has less than about 0.2, alternatively less than about 0.18, alternatively less than about 0.16, alternatively less than about 0.15.
In embodiment, this paper disclosed method produces the improvement that RACCs can cause production efficiency, and reason is the minimizing of catalyst activation time.Do not expect that by one theory the moisture hydrolyzable Cr (VI) that in reactivation process, discharges causes that Cr (VI) is decomposed into Cr (III).In order to alleviate this effect, the time phase that commercial activation method generally prolongs, purpose is to realize that Cr (VI) is stable.Common commercial activation method needs about 36 hours obtaining the target top temperature, and in the time of these temperature maintenance about 12 to about 15 hours scopes, and this produces about 40% Cr (III) conversion to Cr (VI).Do not expect by one theory, but the disclosed basic soln of this paper is handled the consolidation silica dioxide granule, therefore imitation is through between the pot-life that prolongs and the longer analog result that the residence time obtained.Two kinds of methods produce the consolidation of silica dioxide granule, and it has increased matrix strength and when increasing the RACCs pore radius, has reduced surface-area.
When comparing with the similar catalyzer that lacks alkaline purification, RACCs generation as herein described needs the catalyzer of shorter soak time.In one embodiment; When with the other similar catalyzer that lacks other alkaline purification relatively the time, the soak time of RACC as herein described can reduce and is equal to or greater than about 10% or be equal to or greater than about 25% or be equal to or greater than about 50% or be equal to or greater than about 70%.
Embodiment
The present invention is described by generality, and the following example is presented as the specific embodiment of the invention and its practical is described and advantage.It should be understood that embodiment provides and be not intended to limit by any way the detailed description that accompanying claims is followed through elaboration." Quantachrome Autosorb-6Nitrogen Pore Size Distribution Instrument " is used to measure the surface-area and the pore volume of carrier.This equipment is from Quantachrome Corporation of Syosset, and N.Y. obtains.
Embodiment 1
The influence of other catalyzer to activatory catalyzer final quantity loaded in research in catalyst activator.Three catalyst samples, called after sample 1,2 and 3, the different amounts with 150 pounds of (1bs), 450lbs and 1050lbs are fed to activator respectively.Acvator is the 48-in activator.Use catalyzer EP 30X or 969MPI, it can be respectively available from Inneos and W.R.Grace.
Each sample is activated at 1560 ° of F to 1575 ° of F of TR then, and the time length is 12 hours, and slope is 2.5 ° of F/min, 0.21ft/sec.The result is summarized in table 1.
Table 1
The result shows that the increase that Cr (VI) transforms with loaded catalyst reduces.Then, the polymerization activity of detecting catalyst sample in the bench scale reactor drum.
Aggregation test carries out in 2.2 liters of steel reactor that are equipped with the whisking appliance peculiar to vessel that rotates with 400rpm.The steel chuck that contains the methyl alcohol that seethes with excitement that the reactor drum quilt is connected with the steel condensing surface surrounds.The boiling point of methyl alcohol is controlled through the nitrogen pressure that change puts on condensing surface and the chuck, and it is down auxiliary control electronics, makes temperature accurately be controlled in half degree centigrade.Only if having saidly in addition, a small amount of (common 0.01 to 0.10 gram) solid catalyst at first is packed to dry reactor under nitrogen.Next step, 1.2 liters of Trimethylmethane liquid is loaded and reactor drum is heated to 105 ℃ of specified temperature.Last ethene is added into reactor drum with the coupling fixed pressure, common 550psig, and this pressure is kept in experimentation.Make the specified time that stir to continue, about one hour usually, and get into reactor drum through record and write down activity with the ethylene stream of keeping fixation pressure.At the appointed time, stop ethylene stream and reactor drum and slowly reduce pressure and open to reclaim the granular polymer powder.In all cases, reactor drum cleans, and has no the sign of wall dirt, coating or other form dirt.Then, take out polymer powder and weighing.Activity is appointed as the polymkeric substance gram number of every gram solid catalyst generation of per hour filling.
The physical properties of the polymkeric substance of catalyst activity and generation is shown in Fig. 2 and 3.Fig. 2 is the drawing of polymer melt index as the function of catalyst productivity.As shown in Figure 2, polymer melt index reduces with the increase of catalyst charge amount.Fig. 3 is the drawing as the function of polymer melt index of high-load melt index and melt index ratio (HLMI/MI ratio).With reference to figure 3, along with the catalytic amount increase of filling, resin elasticity also is affected.Particularly, increase, observe HLMI/MI ratio and reduce with loaded catalyst.To sum up, these results show that filling more catalyzer to activator does not produce and has more active catalyzer.
Embodiment 2
Research tilts to rise to the effect that shortens the residence time after the target activation temperature in the catalyst activation process.In commercial reactor, carry out several tests, wherein in catalyst sample activatory process, foreshortened to 2 hours from 12 hours 1450 ° of F following residence time of temperature.The result is shown in Fig. 4.Catalyst sample is used to produce polymer compsn subsequently, and the MI of polymkeric substance and HLMI such as embodiment 1 said mensuration.With reference to figure 4, observe when the target activation temperature residence time when 12 hours are reduced to 2 hours, polymer melt index reduces.
Also observe and shorten the residence time and influence elasticity, as shown in Figure 5, wherein with reduction in the target following residence time of activation temperature, the reduction of polymkeric substance HLMI/MI ratio.The result is presented at and shortens residence time generation under the target activation temperature not by abundant activatory catalyzer.
Use 1500 ° of F of higher target temperature to carry out similar test, with of the effect of research comparatively high temps to the amount of the catalyzer that is activated.The result who observes under 1450 ° of F situation of result and target temperature is similar, and promptly catalyzer is not by abundant activation.
Embodiment 3
Use comprises the catalyzer of silica-titania carrier, and the research alkaline purification is to the effect of catalyst activation process.Prepare three kinds of silica-titania hydrogel sample, called after sample 4,5 and 6.Sample 4 is not handled with basic soln, and sample 5 and 6 is used NH
4OH handled 28 hours at 80 ℃.All samples comes drying through in n-propyl alcohol, carrying out final rinsing then, then 800 ℃ of times that are activated 6 hours.Measure surface-area (SA), pore volume (PV) and the pore radius of catalyst sample.Catalyzer is used to produce polymer compsn, and is of embodiment 1, and measures melt index (MI), high-load melt index (HLMI) and the HLMI/MI ratio of the polymkeric substance of polymerization catalyst activity and generation, and the result lists in table 2.
Table 2
As shown in table 2, the alkaline purification of silica-titania hydrogel reduces surface-area and has increased the pore radius of catalyzer.Show the melt index that increases from the polymkeric substance of the Catalyst Production of these alkaline purifications.Observe polymkeric substance HLMI/MI ratio and only reduce slightly, although the very big increase of melt index.Therefore, this trend shows the increase of polymer elasticity.
Embodiment 4
Research changes the effect of drying means to catalyst activation.Prepare two silica-titania hydrogel sample, called after sample 7 and 8.Sample 7 is not handled with basic soln, and sample 8 is used NH
4OH handled 28 hours at 80 ℃.Right latter two sample in baking oven with time of 8 hours of temperature drying of 110 ℃, then in 6 hours time of 800 ℃ of activation.Measure surface-area (SA), pore volume (PV) and the pore radius of these catalyst samples.Catalyzer is used to produce polymeric composition, and is of embodiment 1, and measures melt index (MI), high-load melt index (HLMI), HLMI/MI ratio and the a-eta of polymeric composition.These results are shown in table 3.
Table 3
The result shows that the melt index with the polymerization sample (sample 8) of alkaline purification preparation increases, and observed among the trend of catalyst surface area and pore radius and polymer melt index and the embodiment 3 those are similar.
Although embodiment of the present invention shows and describe, can make amendment and do not depart from spirit of the present invention and instruction it.Embodiment as herein described only is exemplary, does not attempt restriction.Disclosed many variations of the present invention of this paper and modification are possible and fall in the scope of the present invention.When numerical range or restriction when clearly explaining, these expression scopes or restriction should be understood to include iteration scope or the restriction of the similar amt that falls into clear and definite express ranges or restriction (for example about 1 to about 10 comprises 2,3,4 or the like; Comprise 0.11,0.12,0.13 or the like greater than 0.10).For example, as long as openly have lower limit R
LWith upper limit R
UNumerical range, any numeral that falls into this scope is specifically disclosed.Especially, the following column of figure in scope is by concrete open: R=R
L+ k* (R
U-R
L); Wherein k is the variable that percent 1 to percent 100 scopes have percent 1 increments, promptly k be percent 1, percent 2, percent 3, percent 4, percent 5 ... percent 50, percent 51, percent 52 ..., percent 95, percent 96, percent 97, percent 98, percent 99 or percent 100.In addition, as above definition, also open by any numerical range that two R numerals limit by particularly.For any key element of claim, the use of term " randomly " intention be mean subject element be needs or be unwanted alternatively.Two kinds are selected intention is within the scope of the claims.More the term of wide region such as the use that comprises, comprises, has or the like be interpreted as providing more the close limit term such as by ... form, basically by ... form, in fact by ... composition or the like support.
Therefore, protection domain is not by above-mentioned specification sheets restriction, but only by the appended claims restriction, this scope comprises all Equivalents of claims theme.Each incorporates specification sheets with each claim into embodiment of the present invention.Therefore, claims are to further describe and are the increases to embodiment of the present invention.The discussion of reference is not to recognize that it is a prior art of the present invention in the background technology, particularly possibly have the application's priority date any reference of open day afterwards.The open of all patents, patented claim and the publication that this paper quotes is incorporated into this by reference, its degree for they be described herein provide on exemplary, the program or other is additional in detail.
Claims (12)
1. prepare the method for catalyzer, it comprises:
Aging silica supports is to produce alkali aged silica supports in basic soln;
Before aging, in weathering process, after aging or its combination chromium is added into said silica supports;
The said basic soln of from said alkali aged silica supports, removing at least a portion is to produce the exsiccant silica supports; And
The said silica supports of activation is to produce catalyst composition, and wherein the said surface of silica support of the aging reduction of alkali is long-pending extremely less than 50% of original value, and wherein said silica supports has less than 300m
2The surface-area of/g, and the activation of wherein said silica supports is carried out the time durations less than 8 hours with the batch that is equal to or greater than 500lbs.
2. the described method of claim 1, wherein said wearing out carried out 60 ℃ to 90 ℃ temperature.
3. the described method of claim 1, the pH that wherein said basic soln has is 8 to 13.
4. the described method of claim 1, wherein said wearing out carried out at 1 to 24 hour time durations.
5. the described method of claim 1 is wherein removed the said basic soln of at least a portion and is further comprised and alkali aged carrier is contacted the said alkali aged of heated drying carrier, spraying drying said alkali aged carrier or its combination with organic solvent.
6. the described method of claim 1, wherein commercial activation alkali aged compsn comprise that further the said compsn of heating is to the temperature that is equal to or greater than 700 ℃.
7. the described method of claim 1, wherein said silica supports further comprises titanium oxide.
8. prepare the method for polymkeric substance, it comprises:
Use each described method of claim 1-7 to prepare catalyzer;
Said catalyzer and at least a monomer are being suitable for producing at conversion zone under the condition of polymkeric substance and are contacting; And
Reclaim said polymkeric substance.
9. the described method of claim 8, wherein said polymkeric substance comprise that having density is the Vilaterm greater than 0.945g/cc.
10. the described method of claim 9; Wherein said polymkeric substance has 0.1 to 10 melt index; Wherein melt index is meant according to ASTM D 1238 and measures; When in 10 minutes, standing the power of 2160 grams for 190 ℃, can be extruded the amount of the polymkeric substance in the extrusion rheometer hole through 0.0825 inch diameter.
11. the described method of claim 10, wherein said polymkeric substance have the CY-a value less than 0.2.
12. the described method of claim 11, it further comprises the said Vilaterm of blowing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/963,530 US8183173B2 (en) | 2007-12-21 | 2007-12-21 | Fast activating catalyst |
| US11/963,530 | 2007-12-21 | ||
| PCT/US2008/013497 WO2009085100A2 (en) | 2007-12-21 | 2008-12-09 | Fast activating catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101903419A CN101903419A (en) | 2010-12-01 |
| CN101903419B true CN101903419B (en) | 2012-12-05 |
Family
ID=40517736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801219822A Active CN101903419B (en) | 2007-12-21 | 2008-12-09 | Fast activating catalyst |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US8183173B2 (en) |
| EP (2) | EP2231722B1 (en) |
| KR (1) | KR101524330B1 (en) |
| CN (1) | CN101903419B (en) |
| AR (1) | AR069713A1 (en) |
| AU (1) | AU2008343937A1 (en) |
| BR (1) | BRPI0821766B1 (en) |
| CA (1) | CA2710163C (en) |
| CL (1) | CL2008003747A1 (en) |
| ES (2) | ES2668368T3 (en) |
| HU (1) | HUE039190T2 (en) |
| MX (1) | MX2010006971A (en) |
| WO (1) | WO2009085100A2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8183173B2 (en) | 2007-12-21 | 2012-05-22 | Chevron Phillips Chemical Company Lp | Fast activating catalyst |
| JP5746144B2 (en) * | 2010-03-17 | 2015-07-08 | 出光興産株式会社 | Olefin oligomerization catalyst |
| US8396600B2 (en) | 2010-07-23 | 2013-03-12 | Chevron Phillips Chemical Company Lp | Prediction and control solution for polymerization reactor operation |
| US8399580B2 (en) | 2010-08-11 | 2013-03-19 | Chevron Philips Chemical Company Lp | Additives to chromium catalyst mix tank |
| US9023967B2 (en) * | 2011-11-30 | 2015-05-05 | Chevron Phillips Chemical Company Lp | Long chain branched polymers and methods of making same |
| US9096699B2 (en) * | 2011-12-02 | 2015-08-04 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US9376511B2 (en) | 2013-03-13 | 2016-06-28 | Chevron Phillips Chemical Company Lp | Polymerization catalysts and polymers |
| CN105658686A (en) * | 2013-06-24 | 2016-06-08 | 沙特基础工业公司 | Titanated chromium-based catalysts to produce high density polyethylene |
| US20150050742A1 (en) * | 2013-08-16 | 2015-02-19 | Cdti | Analysis of Occurrence of Corrosion Products with ZPGM and PGM Catalysts Coated on Metallic Substrates |
| US10213766B2 (en) | 2015-09-18 | 2019-02-26 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US9988468B2 (en) | 2016-09-30 | 2018-06-05 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US11267914B2 (en) | 2016-12-29 | 2022-03-08 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US10654953B2 (en) | 2016-12-29 | 2020-05-19 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US20200369803A1 (en) | 2016-12-29 | 2020-11-26 | Chevron Phillips Chemical Company Lp | Methods of Preparing a Catalyst |
| US10287369B2 (en) | 2017-04-24 | 2019-05-14 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US10513570B2 (en) | 2017-11-17 | 2019-12-24 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| US10323109B2 (en) | 2017-11-17 | 2019-06-18 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst utilizing hydrated reagents |
| US10543480B2 (en) | 2018-04-16 | 2020-01-28 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst utilizing hydrated reagents |
| US11266976B2 (en) * | 2018-04-16 | 2022-03-08 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst with low HRVOC emissions |
| US10722874B2 (en) | 2018-04-16 | 2020-07-28 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst utilizing hydrated reagents |
| WO2020094714A1 (en) * | 2018-11-08 | 2020-05-14 | Rhodia Operations | Precipitated silica and process for its manufacture |
| GB201903452D0 (en) * | 2019-03-13 | 2019-04-24 | Lucite Int Uk Ltd | A catalyst and a process for the production of ethylenically unsaturated carboxylic acids for esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547557A (en) * | 1984-07-09 | 1985-10-15 | Phillips Petroleum Company | Silica-titania cogel from two-step hydrolysis |
| CN1964787A (en) * | 2004-05-12 | 2007-05-16 | 切弗朗菲利浦化学公司 | Methods of activating chromium catalysts |
Family Cites Families (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248179A (en) | 1962-02-26 | 1966-04-26 | Phillips Petroleum Co | Method and apparatus for the production of solid polymers of olefins |
| US3362946A (en) | 1964-06-01 | 1968-01-09 | Phillips Petroleum Co | Method of treating supported chromium oxide catalyst and polymerization therewith |
| US3281405A (en) | 1964-10-05 | 1966-10-25 | Phillips Petroleum Co | Catalyst and process for polymerizing ethylene |
| US3446754A (en) | 1965-12-03 | 1969-05-27 | Nat Distillers Chem Corp | Catalyst activation |
| US3629216A (en) | 1968-05-14 | 1971-12-21 | Mitsubishi Chem Ind | Process for the polymerization of olefins |
| US3806500A (en) | 1972-07-21 | 1974-04-23 | Union Carbide Corp | Polymerization with thermally aged catalyst |
| US4022580A (en) | 1973-05-07 | 1977-05-10 | Phillips Petroleum Company | Catalyst activation |
| US3976632A (en) | 1974-12-04 | 1976-08-24 | Phillips Petroleum Company | Reactivation of organochromium olefin polymerization catalyst in presence of oxygen |
| US4041224A (en) | 1975-11-19 | 1977-08-09 | Chemplex Company | Catalyst, method and polymerization processes |
| US4151122A (en) | 1977-12-05 | 1979-04-24 | Phillips Petroleum Company | Reduction and reoxidation of cogel or self-reduced catalyst |
| US4296001A (en) | 1980-02-06 | 1981-10-20 | Phillips Petroleum Company | Titanium impregnated silica-chromium catalysts |
| US4397769A (en) | 1981-04-02 | 1983-08-09 | Phillips Petroleum Company | Olefin polymerization catalyst |
| US4501885A (en) | 1981-10-14 | 1985-02-26 | Phillips Petroleum Company | Diluent and inert gas recovery from a polymerization process |
| US4405501A (en) | 1982-01-20 | 1983-09-20 | Phillips Petroleum Company | Aging of chromium-containing gel at high pH |
| US4436882A (en) | 1982-01-20 | 1984-03-13 | Phillips Petroleum Company | Polymerization process utilizing a catalyst prepared by aging of a chromium-containing gel at high pH |
| US4588790A (en) | 1982-03-24 | 1986-05-13 | Union Carbide Corporation | Method for fluidized bed polymerization |
| US5200478A (en) | 1983-04-04 | 1993-04-06 | Solvay S.A. | Method for activating supported chromium oxide catalysts and olefin polymerization process carried out therewith |
| US4981831A (en) * | 1988-07-25 | 1991-01-01 | Phillips Petroleum Company | Twice-aged porous inorganic oxides, catalysts, and polymerization processes |
| US5006506A (en) | 1989-12-21 | 1991-04-09 | Mobil Oil Corporation | Modified chromium-containing catalyst composition for polymerizing olefins and method of preparing the catalyst composition |
| US5565175A (en) | 1990-10-01 | 1996-10-15 | Phillips Petroleum Company | Apparatus and method for producing ethylene polymer |
| US5575979A (en) | 1991-03-04 | 1996-11-19 | Phillips Petroleum Company | Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator |
| US5183792A (en) | 1991-11-26 | 1993-02-02 | Allied-Signal Inc. | Catalyst for making polyethylene |
| US5352749A (en) | 1992-03-19 | 1994-10-04 | Exxon Chemical Patents, Inc. | Process for polymerizing monomers in fluidized beds |
| US5436304A (en) | 1992-03-19 | 1995-07-25 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
| US5576263A (en) * | 1993-12-28 | 1996-11-19 | Phillips Petroleum Company | Chromium catalyst compositions and ethylene polymerization processes therewith |
| US5455314A (en) | 1994-07-27 | 1995-10-03 | Phillips Petroleum Company | Method for controlling removal of polymerization reaction effluent |
| EP0857737A1 (en) | 1997-02-07 | 1998-08-12 | Fina Research S.A. | Production of polyethylene having impact resistance |
| EP0882740A1 (en) | 1997-06-06 | 1998-12-09 | Fina Research S.A. | Titanated chromium-based catalysts to produce polyethylene exhibiting better environmental stress crack resistance |
| US6239235B1 (en) | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
| KR100531628B1 (en) | 1998-03-20 | 2005-11-29 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Continuous slurry polymerization volatile removal |
| US6204346B1 (en) | 1998-12-17 | 2001-03-20 | Phillips Petroleum Co. | Polymerization process |
| US6262191B1 (en) | 1999-03-09 | 2001-07-17 | Phillips Petroleum Company | Diluent slip stream to give catalyst wetting agent |
| BE1012566A3 (en) | 1999-03-23 | 2000-12-05 | Solvay | Method for producing polymers of ethylene. |
| DE19914751A1 (en) | 1999-03-31 | 2000-10-05 | Elenac Gmbh | Process and device for the continuous treatment of catalysts and catalyst supports |
| DE19914752A1 (en) | 1999-03-31 | 2000-10-05 | Elenac Gmbh | Thermal treatment of catalyst material for polyolefin production involves discontinuous activation and/or calcination by heating, tempering and then cooling outside the reactor, with a constant reactor temperature |
| EP1162210A1 (en) | 2000-06-08 | 2001-12-12 | ATOFINA Research | Multimodal polyethylene obtained with multilayer chromium catalyst |
| US7381778B2 (en) | 2002-06-06 | 2008-06-03 | Exxonmobil Chemical Patents Inc. | Method of preparing a treated support |
| US7223823B2 (en) | 2002-06-06 | 2007-05-29 | Exxon Mobil Chemical Patents Inc. | Catalyst system and process |
| US7384885B2 (en) | 2003-03-31 | 2008-06-10 | Exxonmobil Chemical Patents Inc. | Catalyst activation and resins therefrom |
| US8183173B2 (en) | 2007-12-21 | 2012-05-22 | Chevron Phillips Chemical Company Lp | Fast activating catalyst |
-
2007
- 2007-12-21 US US11/963,530 patent/US8183173B2/en active Active
-
2008
- 2008-12-09 EP EP08869028.4A patent/EP2231722B1/en active Active
- 2008-12-09 BR BRPI0821766-1A patent/BRPI0821766B1/en active IP Right Grant
- 2008-12-09 EP EP16153015.9A patent/EP3042919B1/en active Active
- 2008-12-09 ES ES16153015.9T patent/ES2668368T3/en active Active
- 2008-12-09 WO PCT/US2008/013497 patent/WO2009085100A2/en active Application Filing
- 2008-12-09 MX MX2010006971A patent/MX2010006971A/en active IP Right Grant
- 2008-12-09 CN CN2008801219822A patent/CN101903419B/en active Active
- 2008-12-09 KR KR1020107013663A patent/KR101524330B1/en active IP Right Grant
- 2008-12-09 AU AU2008343937A patent/AU2008343937A1/en not_active Abandoned
- 2008-12-09 CA CA2710163A patent/CA2710163C/en active Active
- 2008-12-09 HU HUE16153015A patent/HUE039190T2/en unknown
- 2008-12-09 ES ES08869028.4T patent/ES2573938T3/en active Active
- 2008-12-16 AR ARP080105472A patent/AR069713A1/en active IP Right Grant
- 2008-12-16 CL CL2008003747A patent/CL2008003747A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547557A (en) * | 1984-07-09 | 1985-10-15 | Phillips Petroleum Company | Silica-titania cogel from two-step hydrolysis |
| CN1964787A (en) * | 2004-05-12 | 2007-05-16 | 切弗朗菲利浦化学公司 | Methods of activating chromium catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2008343937A1 (en) | 2009-07-09 |
| BRPI0821766B1 (en) | 2018-08-14 |
| EP2231722B1 (en) | 2016-03-23 |
| EP3042919A3 (en) | 2016-08-24 |
| ES2573938T3 (en) | 2016-06-13 |
| ES2668368T3 (en) | 2018-05-17 |
| AR069713A1 (en) | 2010-02-10 |
| WO2009085100A3 (en) | 2009-10-22 |
| MX2010006971A (en) | 2010-10-05 |
| CL2008003747A1 (en) | 2010-12-24 |
| EP3042919A2 (en) | 2016-07-13 |
| KR101524330B1 (en) | 2015-05-29 |
| CN101903419A (en) | 2010-12-01 |
| WO2009085100A2 (en) | 2009-07-09 |
| EP3042919B1 (en) | 2018-02-14 |
| EP2231722A2 (en) | 2010-09-29 |
| CA2710163C (en) | 2016-04-05 |
| US8183173B2 (en) | 2012-05-22 |
| BRPI0821766A2 (en) | 2015-06-16 |
| HUE039190T2 (en) | 2018-12-28 |
| CA2710163A1 (en) | 2009-07-09 |
| US20090163681A1 (en) | 2009-06-25 |
| KR20100109909A (en) | 2010-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101903419B (en) | Fast activating catalyst | |
| EP2247630B1 (en) | Modified chromium-based catalysts and polymerization processes for using the same | |
| US7700516B2 (en) | Methods of preparing a polymerization catalyst | |
| CN103130933A (en) | Methods of preparing a catalyst | |
| CN104045746A (en) | Polymerization Catalysts and Polymers | |
| JPH01213312A (en) | Catalyst composition for polymerizing alpha- olefin and polymerization of alpha-olefin thereby | |
| EP3757139A1 (en) | Polyethylene | |
| CN116419932A (en) | Particle size control of metallocene catalyst systems in loop slurry polymerization reactors | |
| CN102356098B (en) | Methods of preparing a polymerization catalyst | |
| CN112673032B (en) | Method for preparing supported chromium catalysts with enhanced polymerization activity | |
| EP2146799B1 (en) | Methods of preparing a polymerization catalyst | |
| WO2010063444A1 (en) | Polyethylene for the production of open head drums | |
| US10266618B2 (en) | Chromium-based catalyst compositions for olefin polymerization | |
| WO2013159895A1 (en) | A process for the polymerisation of ethylene | |
| EP3223943B1 (en) | Composition comprising particles | |
| BR112021005598B1 (en) | PROCESSES FOR PRODUCING FLUORINATED SOLID OXIDES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |